Treatment of hydrocarbon oils



Patented May 12, 1936 PATENT oFFlCE I 2,040, 95 TREAT-DENT 0F OILS. Jacque C. Morrciland Gustav Eglofl, Chicago- IlL, assignors,

by mesne assignments, to Uni: versal Oil Products Company,

Chicago, 111., a

corporation of Delaware No Drawing. Application December Serial No. 582,156. Renewed April 4 Claim. This invention relates to the treatment of hydrocarbon oils and refers more particularly to the treatment of low boiling distillates produced in the cracking of heavier higher boiling fractions.

More specifically the invention has reference to a process for treating hydrocarbon mixtures undergoing decomposition and conversion reactions or the lower boiling vaporous products of these reactions to produce substantial amounts of compounds which add materially to the anti-knock value of the gasoline finally produced from the process.

While the cracking process as at present generally practiced in the petroleum industry tends to the production of gasolines having anti-knock characteristics superior to those possessed by corresponding gasoline fractions produced by the straight run distillationof crude 'petroleums, it

may frequently happen that the production of a cracked gasoline of a knock rating rendering it saleable as a premium motor fuel may entail the use of relatively severe cracking conditions with attendant increased losses in fixed gases and coke and a decrease in the overall yield of the desired product. In the majority of cases for any given stock charged to the cracking process there exists an optimum set of conditions for. producing a maximum yield of gasoline of good anti-knock value, the use of more severe conditions, while they may produce gasoline boiling range fractions closely approximating a mixture of aromatic hydrocarbons in composition, producing not only excessive gas losses but a very material lowering in yield of gasoline so that in this respect it may be stated that the production of increased yields of anti-knock gasoline by the cracking process is limited by economic considerations.

The present invention has as one of its objects provision of a process by which the economic disadvantages of producing high anti-knock value gasoline by cracking may be offset by the production concurrently in the cracking process of compounds having a specially high anti-knock value so that the product'of the operation considered as a whole is of the high quality desired and the necessary yields are maintained.

In one specific embodiment the invention comprises treating cracked hydrocarbon vapors with halogens to produce halogen derivatives and further treating with ammonia in the presence of catalysts to produce amines to increase the antiknock value of gasoline produced from the va-' pors. The halo'genation of cracked hdyrocarbon vapors of approximate gasoline boiling point range will follow a course depending upon the chemical composition of the vapors, the temperature and pressure of treatment and the presence of catalytic material, as well as the amount of halogen and the particular halogen used. since such vapor mixtures include representatives of the principal hydrocarbon groups, that is, paraflins, olefins, naphthenes and aromatics in varying Droportions, the ease of halogenation will depend to some extent upon the percentage of the unsaturated compounds present. For example, in cracked vapor mixtures containing relatively high percentages of oleflns, the addition of halogen may proceed with great rapidity independent of catalytic influences and light and electrical effects. when the vapors contain larger percentages of saturated compounds of the straight chain 1 and cyclic series, suiiicienthalogenation may involve the use of catalysts such as iron, aluminum, zinc, etc., or their halid The degree of halogenation which it is best to employ in any particular case will depend upon the type of amines,

which are produced from the halogenated derivatives in the succeeding treatment with ammonia so that the selection of exact quantities oi reagents and conditions of operation will be usually best determined by trial runs. While the individual reactions occurring between the hydrocarbons and the treating reagents are n complicated owing to the great variety carbon compounds present in the original mixture, it is possible to represent the net result by equations such as the following:

RCl+NH,=kRNI-I;+HCl Numerous metallic catalysts may be employed such as the heavy metals, iron, nickel, cobalt,

zinc, cadmium, copper, mercury, chromium, vanadium, etc., and their oxides and of hydro- MM compoun the invention.

I mum'surface action.

saitacopper saltsnrchascoppermlfateoroopper chloride being lection of a particular catalyst for any given set oi conditions the operator will be best guided by experience though it may be mentioned have givenuniformly good results in a large'number of cases.

be found advantageous to utiline the catalysts mixed with or supported upon relaflvely inert spacing 3 Several alternativemethods ofoperationare possible. and are comprised within the scope of As a general rule.'the conditions under whichthe general reactions are brought. about correspond tothese of cracked vapors undergoing fractionation I under super-atmos-. pheric pressure following the, reaction zone of a cracking process, these conditions invoivins temperatures of from approximately 800- to 800' 1". -and pressures inJhe approximate range of 100 to 400 pounds per square-inch. Accordinl to one method of operation'the vapors entering a primary iractionator or separator may receive increments respectively of=- halogen such as. forexample chlorine andat approximately the same point the properfamount of ammonia, the vapor mixture then beingpassed over or through catalytic material of suitable character. Preferably the vapors are subsequently fractionated to pro duce gasoline of desired boiling point range containing the amines produced by the reaction Aniline'ia concentration above described and refluxes which may be returnedtothe reaction zone of the process for further conversion. z

'The relative eifect on the anti-knock value of gasoline of amines of the alkyl and 'aryl' groups respectively'is indicated by the following table which shows part of I the 'ilgures givenin the International Critical Tables, vol. 2, p. "103..

Relatioe efl'e'cts of some compounds of nitrogen for suppressing detonation in engines to '8960! the fuel by volume tabs or standard of sets. All meosarmnts node 48 with boinwin pin a pmtas, wing kerosene as rm 4 The values can be (more, rexectioe o) mount of v grunts regs red to glee on "on knock eel" equivalent 1 to 1 g., of aniline, and (b) colof the of stole, re aired to give on "antinook effect c ivolent to 1 no of outline. Negative values creator I so (o) Wt. (t) Bel. Compound formula for van moLefleoeet tiveness Aniline. O l 1 55 Oumidine gcm,onctmm.-- 0.96 L51 Monomethylanlline CE"-.- 0.83 1.4

CECJLNHLHH 0.04 1.22

benzene CgBlGgHiNH: 1.14 1.14

M l-o-toluidine- QCHICOHiNECEI- 1.15 1.13 Diethylamine rHrhNH 1.50 0. 405 Dietbylaniline----. .lIrN 0,31- 6.1 v 0.24 .D y e CE|N CH5); 6.2 0.21- 60 Ethylamine.---;. csHs 2.4 0.2)

ylamins... com-N-.. 7.96 0.14'

'Avcage of 0-, m-, and

I or the halogens chlorine, bromine, iodine and -fluorine which may be employed alone or inada,oso, sos

inthelimitsofeoonommmchadditionsbeing I specially adaptable. In the sestated that the materialtoinsuremaxi-* results. For example, cracked vapors may be desulphurised to a considerable extent within the capacity ofthe metallic contact masseither to the extent of merely, sweetening the vapors by conversion of mercaptans to dlsulphides or further desulphurizing action mayoccur. The extent of these reactions will depend'upon the chemical character ofthe crackedvapors being treated, thereIatiVe amoimts of. used and other conditions of operation. I

Theprooess oftheinventionmaybeusedas asingletreatmenton crackedvaporsorincomq bination with preceding, or-succeeding treatments for producing as an overall result a ilnished' product of desired-characteristics. For example, the

vapors may be y special desulphurizing and/or polymerizing steps prior'to the introductionof the reactants for the production of amines and stillfurther vapor phase treatments, suitable ,settling periods or filtering by inert'or adsorbent materials may follow. Inthe majority of instances a finalrectifieation to produce end point gasoline is preferable. lHu'thermore, the

condensed product may require a light ilnal wash-' ing to remove tracesof reactionproducts. v

' As an example of a treatment which may be conducted according'to the process of the invention and the results obtainable therefrom, the

' cracked vapors of approximate gasoline boiling point range coming from the'fractionatorof a cracking process operating on Mid-Continent residuum may be considered. such vapors may be evolved from thefractionator under a pressure of approximately 225 pounds square inch and a temperature M525 1".- Chlorine may be inelected into these vapors at the rate of about 4 pounds per barrel of final distillate'along'with approximately 2 pounds of ammonia, injected perto catalyze the reactions'for the either in concentrated aqueous solution ones the V dry gas, the vapors then being passed throllsha treating chamber containingilnely dividedcop-' of amines, then to settlingandiiltering'cha'm bers andiinaliy to a fra'ctionatcr in which the desired'high anti-knockg'asoline is produced as an overhead fraction. fractionating and contacting these vapors with solid adsorbent materials without the use of chlorine and ammonia upon the vapors according to the process of the invention may have the properties shown in the "untreated column following, while gasoline produced by applying the process of the invention may havethe, propertiesshowninthetreated" column.

'rhegasolineprodimdby- --'li'he yield or munern both casesmaybeapproximately 60% of the residuum processed, with the maximum cracking temperature employed 930 1'. 'with a pressure of pounds per square inch. To produce the octane number by straight cracking and fractionation without the use of special vapor phase treatment according to the process of the invention may entail a reduction in yield to approximately 52%, which is a serious consideration 'in commercial work and might render the process uneconomical. Thus the application of the present invention is shown to have definite commercial value.

The foregoing general description of the process 01 the invention and the example of the results obtainable by one operation thereof is sumcient to enable one skilled in the art to recognize its value but since the exact type of operation may be considerably varied and the amount of reagents also varied in the treatment of different stocks, the process as disclosed is not to be construed in any way as a limitation upon the broad scope of the invention.

we claim as our invention:

1. In the cracking of hydrocarbon oils by heat and pressure wherein cracked vapors containing gasoline are separated from residuum, the method which comprises adding a halogen and ammonia to the cracked gasoline vapors after their separation from the residuum, interacting the halogen, ammonia and a part of the vapors in a vapor zone of the cracking process where the vapors are at a temperature of from 300 to 600 F. to form amino derivatives, and condensing and collecting the gasoline vapors containing the amino derivatives thus formed.

2. In the cracking of hydrocarbon oils by heat and.pressure wherein cracked vapors containing gasoline are separated from residuum, the method which comprises adding a-halogen and ammonia vapors and in a vapor zone 01' the cracking procas where the vapors are at a temperatln'e of from 300 to 600 F. to form amino derivatives, and condensing and collecting the gasoline vapors containing the amino derivatives thus formed.

3. In the cracking of hydrocarbon oilsby heat and pressure wherein cracked vapors containing 1 gasoline are separated from residuum, the method which comprises adding chlorine and ammonia to the cracked ga oline vapors after their separation from the residuum, interacting the chlorine, ammonia and a part of the vapors in a vapor zone of the cracking process where the vapors are at a temperature 01' from 300 to 600 F. to form amino derivatives, and condensing and collecting the gasoline vapors containing the amino derivatives thus formed.

4. In the cracking oi hydrocarbon oils by heat and pressure wherein cracked vapors containing gasoline are separated from residu the method which comprises adding chlorine and ammonia to the cracked gasoline vapors after their separation from the residuum, interacting the chlorine, ammonia and a part of the vapors in the presence of a catalyst having a refining action on the vapors and in a vapor zone of the cracking process where the vapors are at a temperature 01. from 300 to 600 F. to form amino derivatives, and condensing and collecting the gasoline vapors containing the amino derivatives thus formed.

' JACQUE C. MORRELL. GUSTAV EGLOEF'. 

